EP0555080A1 - Carbon composite electrode material - Google Patents
Carbon composite electrode material Download PDFInfo
- Publication number
- EP0555080A1 EP0555080A1 EP93300813A EP93300813A EP0555080A1 EP 0555080 A1 EP0555080 A1 EP 0555080A1 EP 93300813 A EP93300813 A EP 93300813A EP 93300813 A EP93300813 A EP 93300813A EP 0555080 A1 EP0555080 A1 EP 0555080A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon
- composite electrode
- electrode material
- carbon composite
- pyrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 36
- 238000000197 pyrolysis Methods 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 64
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000443 aerosol Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 238000001069 Raman spectroscopy Methods 0.000 claims description 2
- 238000000790 scattering method Methods 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 22
- 229910002804 graphite Inorganic materials 0.000 description 19
- 239000010439 graphite Substances 0.000 description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000008188 pellet Substances 0.000 description 18
- 239000011162 core material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
- 150000001721 carbon Chemical class 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- -1 paradium Chemical compound 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011333 coal pitch coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/125—Carbon
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/127—Metals
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1271—Alkanes or cycloalkanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for manufacturing a carbon composite material. More particularly, it relates to a method for manufacturing a carbon composite electrode material used as a negative electrode active material in lithium secondary batteries.
- the inventors of this application found out and disclosed the fact that outstandingly excellent as the negative electrode active material in lithium secondary batteries was particularly a carbon material of a structure such that its internal layer had high crystallinity and that its surface layer was coated with a carbon having a turbulent layer structure (Japanese Patent Application No. Hei 3-144547).
- the present invention provides a method for manufacturing a carbon composite electrode material which comprises coating the surface of core carbon particles with high crystallinity with a film containing a element of Group VIII metal and depositing and/or covering the surface of resulting coated carbon particles with a carbon material to be formed upon pyrolysis of a hydrocarbon or its derivative.
- Desirable carbon material should be formed by pyrolysis in vapor phase or aerosol state of any hydrocarbon or its derivatives and the crystal structure of the carbon particles are consisted of a mean interlayer spacing of approx. 0.335 - 0.340 nm in the C-axis direction and a ratio of intensity of lower than about 0.4 at 1360 cm ⁇ 1 to that at 1580 cm ⁇ 1 of the argon laser Raman spectra method.
- the element of Group VIII metal should desirably be nickel, cobalt or iron or their alloys and the thickness of the film containing the element 0.1 - 2.0 ⁇ m.
- the carbon composite electrode material is desirable to be employed as a negative electrode active material in lithium secondary batteries.
- the present invention provides a method for manufacturing carbon composite electrode material which is coated by carbon material on the surface of the core carbon particles with high crystallinity, relatively a low temperature, in a short time and in order to increase the specific surface area of the carbon composite.
- the core carbon particles with high crystallinity of the present invention are natural graphite, kish graphite, or carbons obtained by heat treating at such a high temperature as above 2000 °C such a well-known carbon material as petroleum coke or coal pitch coke or the like graphitizing carbons.
- Their mean particle size should desirably be not larger than 100 ⁇ m, particularly about 1 - 20 ⁇ m. If its particle size falls in this range, its utilization rate as an active material is high and the filling density of the negative electrode active material may be made high.
- the mean particle size is given by measuring and averaging the particle sizes distributed per unit volume.
- Its form may include either spherical, flaky crystal or fibrous or their pulverulences, but the spherical or flasky crystal form is preferable.
- the core carbon particles with high crystallinity of the present invention are coated with a film containing a Group VIII metal.
- the elements of Group VIII metal of the present invention include iron, nickel, cobalt, ruthenium, rhodium, paradium, osmium, iridium and platinum and their alloys. Among them, iron, nickel and cobalt are preferable
- the coating methods include electroless plating process or a vapor deposition process of evaporating by heating the aforementioned Group VIII metal held under a highly reduced pressure, and sputtering process to form a metal film by the ion impact, and so on.
- the electroplating process or the electroless plating process is preferable in views of economy and productivity.
- a plating bath is prepared with approx. 20 of NiSO4 ⁇ 7H2O and approx. 25 of NaH2PO2 in ratio by weight with its pH adjusted to approx. 5.0 and the core carbon particles are dipped into this plating bath. Then by adding such a reducing agent as phosphate or sodium hydrogen boride to this plating bath, while holding it at about 90°C, a metal film is formed on the surface of the carbon particles with high crystallinity
- a reducing agent as phosphate or sodium hydrogen boride
- the average thickness of the coated film containing a Group VIII metal should preferably be 0.01 - 2.0 ⁇ m. If it is thinner than 0.01 ⁇ m, its effect as a catalyst is slight, but if thicker than 2.0 ⁇ m, the rates of intercalation and deintercalation into and from the internal carbon material are slow.
- a carbon material is formed, deposited and/or covered through pyrolysis of a hydrocarbon or its derivatives in vapor phase or in the state of aerosol.
- the hydrocarbons and their derivatives include aliphatic or aromatic or alicyclic hydrocarbons and their partly substituents (halogen atoms, hydroxyl, sulfo, nitro, amino and carboxyl groups, etc.).
- methane, ethane and propane are preferable, because they are not expensive, their waste gases are readily treatable and they are not liable to corrode the pyrolysis furnace.
- any of the aforementioned hydrocarbons or its derivatives in gas phase or in aerosol state is (are) fed to a carbon pyrolysis and depositing apparatus, to be carried onto a film containing a Group VIII metal which is placed on a holder for depositing carbon material.
- the feed rate of the gas phase material or the aerosol is 0.03 - 20 mols/hr and its flow rate 5 - 100 cm/min.
- This pyrolysis is performed at a temperature of approx. 300 - 1300°C, preferably approx. 500 - 1100°C in a noncombustible atmosphere, for example, under reduced pressure or in an inert gas. In this way, a carbon composite electrode material with a particle size of approx. 15 - 50 ⁇ m is obtained.
- this carbon composite electrode material core carbon particles with high crystallinity are coated with a film containing a Group VIII metal and on their film surface, there is further formed a carbon material through pyrolysis and depositing of a hydrocarbon or its derivatives in gas phase or in the aerosol. Accordingly, it has the undermentioned characteristic features.
- the Group VIII metal acts as a catalyst for the pyrolysis reaction of the hydrocarbon or its derivatives in gas phase or in aerosol state
- the carbon material can be relatively formed and deposited at a low temperature and in a short time.
- the carbon material of the surface layer of the carbon composite electrode material is a carbon material formed and deposited through pyrolysis of a hydrocarbon. Therefore, it is a carbon material of the so-called turbulent layer structure which permits easy intercalation and deintercalation of lithium ion, etc.
- the carbon material with turbulent layer structure refers to a material having a crystal structure which gives a mean lattice width of 0.377 nm or larger in its C-axis direction and which gives a ratio of 0.4 or higher of the peak intensity at 1360 cm ⁇ 1 to that at 1580 cm ⁇ 1 of the argon laser Raman spectra.
- a powder (mean particle size 18.0 ⁇ m, average lattice width of 0.3358 nm in the C-axis direction and the peak at 1360 cm ⁇ 1 in its argon laser Raman spectra not observed) of graphite (KS-75, mfd. by Lonza Co.) were taken and coated with nickel by the electroless nickel plating process.
- the powder was subjected to a sensitization treatment as a pretreatment, using MAC-100 (mfd. by Okuno Seiyaku Kogyo K.K.), thoroughly water-rinsed, then subjected to an activation treatment with MAC-200 (mfd.
- the film was formed using TMP Kagaku nickel (mfd. by Okuno Seiyaku Kogyo K.K.) as the plating bath at approx. 35°C, while stirring the bath with a stirrer.
- the mean nickel film thickness was calculated to be 0.79 ⁇ m from the increment of its weight and its mean particle size.
- the graphite coated with nickel film obtained in this way was mounted on a holder of a carbon pyrolysis and depositing apparatus. Then using the carbon pyrolysis and depositing apparatus shown in FIG. 1, the formation, deposition and/or covering of the carbon material through pyrolysis of any hydrocarbon was carried out by the undermentioned procedure.
- argon and propane gases were respectively fed into this apparatus.
- concentration of propane was adjusted to 10 mol%.
- the current velocity of both gases was preset to 12.7 cm/min and propane was fed at a rate of 0.05 mol/hr.
- the graphite coated with the nickel film was mounted and a furnace was installed on the outer circumference of the reactor tube 5.
- the sample holder 6 and the graphite coated with the nickel film were held at a temperature of 750°C, to pyrolysis of the propane fed through a pipe 3 made of Pyrex glass, thereby forming and depositing the carbon material on the surface of the nickel film coating the graphite, yielding particles of a carbon composite electrode material.
- the reaction time at this time was set at approx. 30 min.
- the mean particle size of the carbon composite electrode material obtained at this time was approx. 25.1 ⁇ m, as determined by laser diffraction particle analyzer.
- the observed particles are consisted of the mixture of those cohered each other and those not cohered, since the particles were deposited and cohered each other through the reaction.
- this carbon composite electrode material was mixed with 5% by weight of a polyolefin as a binder. It was then hot-pressed on a nickel mesh at about 120°C and under about 400 kg/cm2, yielding a pellet with an approx. 15 mm dia. This pellet was named test electrode A.
- the carbon composite electrode material was prepared under the similar conditions, except that they were not coated with the nickel film.
- a powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with cobalt by electroless cobalt plating process.
- the powder was dipped in a cobalt plating bath, after subjecting it to the pretreatment and the activation treatment under the similar conditions as in Example 1.
- the plating bath was prepared by mixing 0.13 mol/l of CoCl3 ⁇ 6H2O and 0.05 mol/l of sodium hypophosphite and with this bath, the cobalt was plated on the powder at a temperature of 80°C.
- the plated cobalt film thickness, as measured by the similar method as in Example 1, was approx. 0.51 ⁇ m.
- the carbon material was formed, deposited and/or covered, to prepare the carbon composite electrode material, similarly as in Example 1, except using the graphite coated with the cobalt film obtained in this way.
- the mean particle size of the carbon composite electrode material at this time was found to be about 28.3 ⁇ m, as determined by laser diffraction particle analyzer.
- Example 2 Further a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode B.
- a powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel-iron alloy by electroless nickel-iron plating process.
- the powder was dipped in a nickel-iron alloy plating bath, after subjecting it to the pretreatment and the activation treatment under the similar conditions as in Example 1.
- the plating bath was prepared by mixing 0.05 mol/l of NiSO4 ⁇ 6H2O, 0.05 mol/l of ammonium iron (II) sulfate, 0.16 mol/l of sodium citrate and 0.5 mol/l of ammonium sulfate and with this bath, the powder was plated with nickel-iron at about 90°C.
- the plated film thickness as measured by the similar method as in Example 1, was found to be approx. 0.80 ⁇ m.
- the mean particle size of the carbon composite electrode material at this time was found to be about 28.3 ⁇ m, as determined by observation by laser diffraction particle analyzer.
- a powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel by the nonelectrolytic nickel plating process similarly as in Example 1.
- the formation and deposition of the carbon material was made through pyrolysis of a hydrocarbon by the similar procedure as in Example 1, using the carbon pyrolysis and depositing apparatus shown in FIG. 1. At this time, in place of propane, benzene was used as the raw material hydrocarbon.
- the conditions of the pyrolysis were: The current velocity of the gases 25.5 cm/min, its feed rate 0.15 mol/hr, the reaction temperature approx. 650°C and the reaction time approx. 30 min.
- the mean particle size of the carbon conposite electrode material at this time was found to be abot 29.3 ⁇ m, as determined by laser diffraction particle analyzer.
- Example 2 a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode D.
- a powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel by the electroless nickel plating process similarly as in Example 1.
- the formation and deposition of the carbon material was made through pyrolysis of a hydrocarbon by the similar procedure as in Example 1, using the carbon pyrolysis and depositing apparatus shown in FIG. 1. At this time, in place of propane, 2-dichloroethylene was used as the raw material hydrocarbon.
- the conditions of the pyrolysis were: The flow rate of the gases 18.5 cm/min, its feed rate 0.12 mol/hr, the reaction temperature approx. 650°C and the reaction time approx. 30 min.
- the mean particle size of the carbon conposite electrode material at this time was found to be about 34.5 ⁇ m, as determined by laser diffraction particle analyzer.
- Example 2 a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode E.
- Example 2 a carbon composite electrode material was prepared by forming and depositing a carbon material on the plated particles.
- the mean particle size of the carbon composite electrode material at this time was approx. 14.1 ⁇ m, as determined by laser diffraction particle analyzer.
- Example 2 a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode F.
- a carbon composite electrode material was prepared by forming, depositing and/or covering a carbon material on the plated spherules.
- the mean particle size of the carbon composite electrode material at this time was approx. 12.6 ⁇ m, as determined by laser diffraction particle analyzer.
- Example 2 a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode G.
- the mean thickness of the nickel film at this time was found to be 1.72 ⁇ m and the mean particle size of the carbon composite electrode material was 25.3 ⁇ m.
- Example 1 a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode H.
- test electrodes A through H and the comparative electrode above mentioned charge-discharge tests were carried out in the range of 0 - 2.5 V.
- the working electrode As the working electrode, the test electrodes and the comparative electrode were used and as the counter electrode and the reference electrode, lithium metal was used.
- the electrolyte propylene carbonate having 1 mol/l of LiClO4 dissolved therein was used.
- the charge-discharge test was carryed out in a globe box in an argon atmosphere. The discharge curves obtained at that time were depicted in FIGs. 2 and 3. These graphs indicate that, as compared with the comparative electrode, all of the test electrodes A through H gave higher discharge capacity.
- a carbon material having an inside layer with high crystallinity and an outside layer with turbulent crystal structure could be relatively manufactured at a low temperature and in a short time.
- the charge-discharge capacity and rate was remarkably improved because of larger surface area of the electrode.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Thermal Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Secondary Cells (AREA)
Abstract
Description
- The present invention relates to a method for manufacturing a carbon composite material. More particularly, it relates to a method for manufacturing a carbon composite electrode material used as a negative electrode active material in lithium secondary batteries.
- It was reported that when a certain type of carbon material, of carbon composite electrode materials, is used as a negative electrode active material in lithium secondary batteries, the charge-discharge cycle characteristic and safety of the secondary batteries is excellent (for example, Japanese Patent Unexamined Publication Nos. Sho 63-24555 and Hei 1-311565). This carbon material is manufactured, for example, by chemical vapor deposition (CVD) of a hydrocarbon.
- The inventors of this application found out and disclosed the fact that outstandingly excellent as the negative electrode active material in lithium secondary batteries was particularly a carbon material of a structure such that its internal layer had high crystallinity and that its surface layer was coated with a carbon having a turbulent layer structure (Japanese Patent Application No. Hei 3-144547).
- As manufacturing methods of carbon composite electrode materials, there is available a method of forming and depositing a carbon material through chemical vapor depositon any hydrocarbon or its derivatives on the surface of such a carbon material as graphite used as its core material. In this instance, the deposited carbon material shows a turbulent layer structure. The system needs to be held at about 1000°C for a long period of time so to deposit the carbon material having such a turbulent layer structure. Under such conditions, this method is not practically useful, because a large amount of a tarry product is generated by side reactions.
- The present invention provides a method for manufacturing a carbon composite electrode material which comprises coating the surface of core carbon particles with high crystallinity with a film containing a element of Group VIII metal and depositing and/or covering the surface of resulting coated carbon particles with a carbon material to be formed upon pyrolysis of a hydrocarbon or its derivative.
- Desirable carbon material should be formed by pyrolysis in vapor phase or aerosol state of any hydrocarbon or its derivatives and the crystal structure of the carbon particles are consisted of a mean interlayer spacing of approx. 0.335 - 0.340 nm in the C-axis direction and a ratio of intensity of lower than about 0.4 at 1360 cm⁻¹ to that at 1580 cm⁻¹ of the argon laser Raman spectra method.
- Further, the element of Group VIII metal should desirably be nickel, cobalt or iron or their alloys and the thickness of the film containing the element 0.1 - 2.0 µm.
- Furthermore, the carbon composite electrode material is desirable to be employed as a negative electrode active material in lithium secondary batteries.
-
- FIG. 1 is a schematic diagram of a carbon material pyrolysis and depositing apparatus used in an embodiment of this invention;
- FIG. 2 is a diagrammatic representation of discharging curves for the test electrode A in an embodiment and a comparative electrode; and
- FIG. 3 is a diagrammatic representation of discharging curves for other test electrodes B, C, D, E, F, G and H in embodiments of this invention.
- The present invention provides a method for manufacturing carbon composite electrode material which is coated by carbon material on the surface of the core carbon particles with high crystallinity, relatively a low temperature, in a short time and in order to increase the specific surface area of the carbon composite.
- The core carbon particles with high crystallinity of the present invention are natural graphite, kish graphite, or carbons obtained by heat treating at such a high temperature as above 2000 °C such a well-known carbon material as petroleum coke or coal pitch coke or the like graphitizing carbons. Their mean particle size should desirably be not larger than 100 µm, particularly about 1 - 20 µm. If its particle size falls in this range, its utilization rate as an active material is high and the filling density of the negative electrode active material may be made high. The mean particle size is given by measuring and averaging the particle sizes distributed per unit volume.
- Its form may include either spherical, flaky crystal or fibrous or their pulverulences, but the spherical or flasky crystal form is preferable.
- Further, its desirable crystal structure should have a mean interlayer spacing of 0.335 - 0.340 nm, as determined by the X-ray wide angle diffraction method, and lower than about 0.4 as a ratio of the peak intensity at 1360 cm⁻¹ to that at 1580 cm⁻¹ in the argon laser Raman scattering method. The core carbon particles with high crystallinity of the present invention are coated with a film containing a Group VIII metal. The elements of Group VIII metal of the present invention include iron, nickel, cobalt, ruthenium, rhodium, paradium, osmium, iridium and platinum and their alloys. Among them, iron, nickel and cobalt are preferable
- The coating methods include electroless plating process or a vapor deposition process of evaporating by heating the aforementioned Group VIII metal held under a highly reduced pressure, and sputtering process to form a metal film by the ion impact, and so on. The electroplating process or the electroless plating process is preferable in views of economy and productivity.
- In the electroless nickel plating process, a plating bath is prepared with approx. 20 of NiSO₄·7H₂O and approx. 25 of NaH₂PO₂ in ratio by weight with its pH adjusted to approx. 5.0 and the core carbon particles are dipped into this plating bath. Then by adding such a reducing agent as phosphate or sodium hydrogen boride to this plating bath, while holding it at about 90°C, a metal film is formed on the surface of the carbon particles with high crystallinity For these plating baths and the reducing agents, those prepared and available on the commercial may be utilized (for example, TMP Kagaku nickel: mfd. by Okuno Seiyaku Kogyo K.K.).
- The average thickness of the coated film containing a Group VIII metal should preferably be 0.01 - 2.0 µm. If it is thinner than 0.01 µm, its effect as a catalyst is slight, but if thicker than 2.0 µm, the rates of intercalation and deintercalation into and from the internal carbon material are slow.
- As the film containing a Group VIII metal, a carbon material is formed, deposited and/or covered through pyrolysis of a hydrocarbon or its derivatives in vapor phase or in the state of aerosol. The hydrocarbons and their derivatives include aliphatic or aromatic or alicyclic hydrocarbons and their partly substituents (halogen atoms, hydroxyl, sulfo, nitro, amino and carboxyl groups, etc.). Their actual examples include: methane, ethane, propane, butane, pentane, hexane, cyclohexane, naphthalene, anthracene, pyrene, benzene, toluene, pyridine, allyl benzene, hexamethyl benzene, aniline, phenol, 1,2-dichloroethylene, 1,2-dibromoethylene, 2-butene, acetylene, biphenyl, diphenyl acetylene, styrene, acrylonitrile, pyrrole and thiophene and their derivatives. Of these compounds, methane, ethane and propane are preferable, because they are not expensive, their waste gases are readily treatable and they are not liable to corrode the pyrolysis furnace.
- Any of the aforementioned hydrocarbons or its derivatives in gas phase or in aerosol state is (are) fed to a carbon pyrolysis and depositing apparatus, to be carried onto a film containing a Group VIII metal which is placed on a holder for depositing carbon material. As the reaction conditions at that time, the feed rate of the gas phase material or the aerosol is 0.03 - 20 mols/hr and its flow rate 5 - 100 cm/min. This pyrolysis is performed at a temperature of approx. 300 - 1300°C, preferably approx. 500 - 1100°C in a noncombustible atmosphere, for example, under reduced pressure or in an inert gas. In this way, a carbon composite electrode material with a particle size of approx. 15 - 50 µm is obtained.
- In this carbon composite electrode material, core carbon particles with high crystallinity are coated with a film containing a Group VIII metal and on their film surface, there is further formed a carbon material through pyrolysis and depositing of a hydrocarbon or its derivatives in gas phase or in the aerosol. Accordingly, it has the undermentioned characteristic features.
- First, since the Group VIII metal acts as a catalyst for the pyrolysis reaction of the hydrocarbon or its derivatives in gas phase or in aerosol state, the carbon material can be relatively formed and deposited at a low temperature and in a short time.
- Secondly, a part or all film of the Group VIII metal diffuses into the carbon material formed, deposited and/or covered thereon during the aforementioned pyrolysis, the core carbon particles with high crystallinity are directly covered with the carbon material formed and deposited through pyrolysis.
- Thirdly, the carbon material of the surface layer of the carbon composite electrode material is a carbon material formed and deposited through pyrolysis of a hydrocarbon. Therefore, it is a carbon material of the so-called turbulent layer structure which permits easy intercalation and deintercalation of lithium ion, etc. The carbon material with turbulent layer structure refers to a material having a crystal structure which gives a mean lattice width of 0.377 nm or larger in its C-axis direction and which gives a ratio of 0.4 or higher of the peak intensity at 1360 cm⁻¹ to that at 1580 cm⁻¹ of the argon laser Raman spectra.
- As core carbon particles with high crystallinity, 5.014 g of a powder (mean particle size 18.0 µm, average lattice width of 0.3358 nm in the C-axis direction and the peak at 1360 cm⁻¹ in its argon laser Raman spectra not observed) of graphite (KS-75, mfd. by Lonza Co.) were taken and coated with nickel by the electroless nickel plating process. In forming the nickel film, the powder was subjected to a sensitization treatment as a pretreatment, using MAC-100 (mfd. by Okuno Seiyaku Kogyo K.K.), thoroughly water-rinsed, then subjected to an activation treatment with MAC-200 (mfd. by Okuno Seiyaku Kogyo K.K.), followed by thorough water-rinsing , and thereafter underwent the plating process. The film was formed using TMP Kagaku nickel (mfd. by Okuno Seiyaku Kogyo K.K.) as the plating bath at approx. 35°C, while stirring the bath with a stirrer.
- Since the weight of graphite, after coated with the film, was 10.128 g, the mean nickel film thickness was calculated to be 0.79 µm from the increment of its weight and its mean particle size.
- The graphite coated with nickel film obtained in this way was mounted on a holder of a carbon pyrolysis and depositing apparatus. Then using the carbon pyrolysis and depositing apparatus shown in FIG. 1, the formation, deposition and/or covering of the carbon material through pyrolysis of any hydrocarbon was carried out by the undermentioned procedure.
- Through an argon feeding line 1 and a
propane feeding line 2, argon and propane gases were respectively fed into this apparatus. By operatingneedle valves 3 and 4, the concentration of propane was adjusted to 10 mol%. The current velocity of both gases was preset to 12.7 cm/min and propane was fed at a rate of 0.05 mol/hr. On the other hand, on the sample holder 6 inside the reactor tube 5, the graphite coated with the nickel film was mounted and a furnace was installed on the outer circumference of the reactor tube 5. By thisfurnace 7, the sample holder 6 and the graphite coated with the nickel film were held at a temperature of 750°C, to pyrolysis of the propane fed through apipe 3 made of Pyrex glass, thereby forming and depositing the carbon material on the surface of the nickel film coating the graphite, yielding particles of a carbon composite electrode material. The reaction time at this time was set at approx. 30 min. The mean particle size of the carbon composite electrode material obtained at this time was approx. 25.1 µm, as determined by laser diffraction particle analyzer. However, there is a possibility that the observed particles are consisted of the mixture of those cohered each other and those not cohered, since the particles were deposited and cohered each other through the reaction. - It should be noted that the gas remaining in the reactor tube after the pyrolysis reaction was removed by exhausting through an exhaust facility 9.
- With regard to the crystalline structure of the carbon composite electrode material obtained in this way, results of measurements of its X-ray diffraction and argon laser Raman spectra gave the undermentioned data:
In this case, X-ray by CuKα line was employed for the X-ray diffraction and d represents a mean interlayer spacing. R denotes the ratio of the peak intensity at 1360 cm⁻¹ to that at 1580 cm⁻¹ of the argon laser Raman spectra. - About 30 mg of this carbon composite electrode material was mixed with 5% by weight of a polyolefin as a binder. It was then hot-pressed on a nickel mesh at about 120°C and under about 400 kg/cm², yielding a pellet with an approx. 15 mm dia. This pellet was named test electrode A.
- Using the powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 as the core carbon particles with high crystallinity, the carbon composite electrode material was prepared under the similar conditions, except that they were not coated with the nickel film. When the measurements were taken of the characteristics of the crystal structure obtained in this way under the similar conditions as in Example 1, the results gave the undermentioned data:
The aforementioned interlayer spacing was found to be nearly equal to that of graphite, attesting to the fact that under such conditions as in Example 1, noncrystalline carbon material is hardly formed on the graphite surface. - Measurement results of the specific surface area by the BET method suggested that the carbon composite electrode material of Example 1 has 12 times as large a specific surface area as that of the carbon composite electrode material of Comparative Example 1.
- Further, from about 30 mg of this carbon composite electrode material, a pellet with an approx. 15 mm dia. was obtained by the similar method as in Example 1. This pellet was named comparative electrode.
- A powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with cobalt by electroless cobalt plating process. The powder was dipped in a cobalt plating bath, after subjecting it to the pretreatment and the activation treatment under the similar conditions as in Example 1. The plating bath was prepared by mixing 0.13 mol/l of CoCl₃·6H₂O and 0.05 mol/l of sodium hypophosphite and with this bath, the cobalt was plated on the powder at a temperature of 80°C. The plated cobalt film thickness, as measured by the similar method as in Example 1, was approx. 0.51 µm.
- The carbon material was formed, deposited and/or covered, to prepare the carbon composite electrode material, similarly as in Example 1, except using the graphite coated with the cobalt film obtained in this way. The mean particle size of the carbon composite electrode material at this time was found to be about 28.3 µm, as determined by laser diffraction particle analyzer. The results of the measurements on the characteristics of this crystal structure, as taken under the similar conditions as in Example 1, gave the undermentioned data
- Further a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode B.
- A powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel-iron alloy by electroless nickel-iron plating process. The powder was dipped in a nickel-iron alloy plating bath, after subjecting it to the pretreatment and the activation treatment under the similar conditions as in Example 1. The plating bath was prepared by mixing 0.05 mol/l of NiSO₄·6H₂O, 0.05 mol/l of ammonium iron (II) sulfate, 0.16 mol/l of sodium citrate and 0.5 mol/l of ammonium sulfate and with this bath, the powder was plated with nickel-iron at about 90°C. The plated film thickness, as measured by the similar method as in Example 1, was found to be approx. 0.80 µm. The mean particle size of the carbon composite electrode material at this time was found to be about 28.3 µm, as determined by observation by laser diffraction particle analyzer.
- The carbon material was formed and deposited, to prepare the carbon composite electrode material, similarly as in Example 1, except using the graphite coated with the nickel-iron alloy film obtained in this way. The results of the measurements on the characteristics of this crystal structure, as taken under the similar conditions as in Example 1, gave the undermentioned data:
- Further a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode C.
- A powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel by the nonelectrolytic nickel plating process similarly as in Example 1.
- The formation and deposition of the carbon material was made through pyrolysis of a hydrocarbon by the similar procedure as in Example 1, using the carbon pyrolysis and depositing apparatus shown in FIG. 1. At this time, in place of propane, benzene was used as the raw material hydrocarbon. The conditions of the pyrolysis were: The current velocity of the gases 25.5 cm/min, its feed rate 0.15 mol/hr, the reaction temperature approx. 650°C and the reaction time approx. 30 min. The mean particle size of the carbon conposite electrode material at this time was found to be abot 29.3 µm, as determined by laser diffraction particle analyzer.
-
- Further, a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode D.
- A powder of the graphite (KS-75, mfd. by Lonza Co.) of Example 1 used as the core carbon particles with high crystallinity was coated with nickel by the electroless nickel plating process similarly as in Example 1.
- The formation and deposition of the carbon material was made through pyrolysis of a hydrocarbon by the similar procedure as in Example 1, using the carbon pyrolysis and depositing apparatus shown in FIG. 1. At this time, in place of propane, 2-dichloroethylene was used as the raw material hydrocarbon. The conditions of the pyrolysis were: The flow rate of the gases 18.5 cm/min, its feed rate 0.12 mol/hr, the reaction temperature approx. 650°C and the reaction time approx. 30 min. The mean particle size of the carbon conposite electrode material at this time was found to be about 34.5 µm, as determined by laser diffraction particle analyzer.
-
- Further, a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode E.
- About 5 g of a powder of natural graphite (produced in Madagascar, its mean particle size 6.2 µm, d=0.3363 nm, no peak at 1360 cm⁻¹ in the argon laser Raman spectra observed) used as the core carbon particles with high crystallinity was coated with nickel by the electroless nickel plating process. The pretreatment and the activation treatment for forming the nickel film were similarly performed as in Example 1 and then the powder was submitted to the plating process. A nickel film was formed in the plating bath of a mixture of 30 g/l of NiSO₄·6H₂O, 10 g/l of sodium acetate and 10 g/l of sodium hypophosphite at about 90°C. From the weight of the graphite thus coated, the mean film thickness of the nickel film was calculated to be 0.70 µm.
- Similarly as in Example 1, a carbon composite electrode material was prepared by forming and depositing a carbon material on the plated particles. The mean particle size of the carbon composite electrode material at this time was approx. 14.1 µm, as determined by laser diffraction particle analyzer. The results of the measurements on the characteristics of the crystal structure, as taken under the similar conditions as in Example 1, gave the undermentioned data:
- Further, a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode F.
- About 5 g of mesophase spherules carbonized and further heat-treated at 2800°C (their mean particle size 5.8 µm, d=0.3368 nm and R=0.35) used as the core carbon particles with high crystallinity were coated with nickel by the electroless nickel plating process. Their pretreatment and activation treatment for forming the nickel film were similarly performed as in Example 1 and then the spherules were submitted to the plating process. A nickel film was formed in the plating bath of a mixture of 30 g/l of NiSO₄·6H₂O, 50 g/l of ammonium chloride with 10 g/l of sodium hypophosphite at about 90°C. From the weight of the graphite thus coated, the mean film thickness of the nickel film was calculated to be 0.84 µm.
- Similarly as in Example 1, a carbon composite electrode material was prepared by forming, depositing and/or covering a carbon material on the plated spherules. The mean particle size of the carbon composite electrode material at this time was approx. 12.6 µm, as determined by laser diffraction particle analyzer. The results of the measurements on the characteristics of the crystal structure, as taken under the similar conditions as in Example 1, gave the undermentioned data:
- Further, a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode G.
- A carbon composite electrode material was prepared similarly as in Example 7, except that mesophase spherules which had been carbonized and further heat-treated at 2000 °C (their mean particle size 16.4 µm, d=0.3385 nm, R=0.39) were used as the core carbon particles with high crystallinity. The mean thickness of the nickel film at this time was found to be 1.72 µm and the mean particle size of the carbon composite electrode material was 25.3 µm. The results of the measurements on the characteristics of the crystal structure, as taken under the similar conditions as in Example 1, gave the undermentioned data:
- Further, a pellet with an approx. 15 mm dia. was obtained from about 30 mg of this carbon composite electrode material by the similar method as in Example 1. This pellet was named test electrode H.
- With the test electrodes A through H and the comparative electrode above mentioned, charge-discharge tests were carried out in the range of 0 - 2.5 V. As the working electrode, the test electrodes and the comparative electrode were used and as the counter electrode and the reference electrode, lithium metal was used. As the electrolyte, propylene carbonate having 1 mol/l of LiClO₄ dissolved therein was used. The charge-discharge test was carryed out in a globe box in an argon atmosphere. The discharge curves obtained at that time were depicted in FIGs. 2 and 3. These graphs indicate that, as compared with the comparative electrode, all of the test electrodes A through H gave higher discharge capacity.
- According to this invention, a carbon material having an inside layer with high crystallinity and an outside layer with turbulent crystal structure could be relatively manufactured at a low temperature and in a short time. In cells using the carbon composite electrode material obtained by this manufacturing method as their negative electrode active substance, the charge-discharge capacity and rate was remarkably improved because of larger surface area of the electrode.
Claims (6)
- A method for manufacturing a carbon composite electrode material which comprises coating the surface of core carbon particles with high crystallinity with a film containing a element of Group VIII metal and depositing and/or covering the surface of resulting coated carbon particles with a carbon material to be formed upon pyrolysis of a hydrocarbon or its derivative.
- The method as claimed in Claim 1, wherein the characteristics of the crystal structure of the carbon particles are a mean interlayer spacing of about 0.335 - 0.340 nm in the C-axis direction and a ratio of the peak intensity of lower than about 0.4 at 1360 cm⁻¹ to that at 1580 cm⁻¹ in its argon laser Raman scattering method.
- The method as claimed in Claim 1, wherein the carbon material is formed by pyrolysis of a hydrocarbon or its derivatives in vapor phase or aerosol state.
- The method as claimed in Claim 1, wherein the element of Group VIII metal is nickel, cobalt or iron or their alloys.
- The method as claimed in Claim 1, wherein the thickness of the film containing the element is from 0.1 - 2.0 µm.
- The method as claimed in Claim 1, wherein the carbon composite electrode material is employed as a negative electrode active material in lithium secondary batteries.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1796992 | 1992-02-04 | ||
JP17969/92 | 1992-02-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0555080A1 true EP0555080A1 (en) | 1993-08-11 |
EP0555080B1 EP0555080B1 (en) | 1996-05-15 |
Family
ID=11958565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93300813A Expired - Lifetime EP0555080B1 (en) | 1992-02-04 | 1993-02-04 | Carbon composite electrode material |
Country Status (4)
Country | Link |
---|---|
US (1) | US5595838A (en) |
EP (1) | EP0555080B1 (en) |
JP (1) | JP2999085B2 (en) |
DE (1) | DE69302596T2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0833398A1 (en) * | 1996-09-24 | 1998-04-01 | PETOCA, Ltd | Surface graphitized carbon material, process for producing the same and negative electrode for lithium-ion secondary battery using the carbon material |
EP1045465A2 (en) * | 1999-04-14 | 2000-10-18 | Sony Corporation | Material for negative electrode and nonaqueous-electrolyte battery incorporating the same |
EP1422773A1 (en) * | 1993-10-08 | 2004-05-26 | Electro Energy, Inc. | Metal coated active material particles for battery electrodes |
US7776472B2 (en) | 2006-01-16 | 2010-08-17 | Ls Mitron Ltd. | Anode material for secondary battery, method for producing the same and secondary batteries using the same |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06229155A (en) * | 1992-01-13 | 1994-08-16 | C & M Technology Inc | Security lock mechanism |
US5776610A (en) * | 1993-02-03 | 1998-07-07 | Sharp Kabushiki Kaisha | Carbon composite electrode material and method of making thereof |
US20100021800A1 (en) * | 2008-07-24 | 2010-01-28 | Rachid Yazami | Carbon cathodes for fluoride ion storage |
US6030726A (en) * | 1996-06-17 | 2000-02-29 | Hitachi, Ltd. | Lithium secondary battery having negative electrode of carbon material which bears metals |
US5908715A (en) * | 1997-05-30 | 1999-06-01 | Hughes Electronics Corporation | Composite carbon materials for lithium ion batteries, and method of producing same |
JP3949303B2 (en) * | 1998-03-20 | 2007-07-25 | 三星エスディアイ株式会社 | Carbon material for negative electrode of lithium secondary battery and lithium secondary battery using the same |
KR100315232B1 (en) * | 1999-02-24 | 2001-11-26 | 김순택 | Negative active material for lithium secondary battery and method of preapring the same |
CA2270771A1 (en) | 1999-04-30 | 2000-10-30 | Hydro-Quebec | New electrode materials with high surface conductivity |
KR100354226B1 (en) * | 1999-09-01 | 2002-09-27 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
JP3103356B1 (en) * | 1999-09-28 | 2000-10-30 | 株式会社サムスン横浜研究所 | Negative electrode material for lithium secondary battery, electrode for lithium secondary battery, method for producing lithium secondary battery and negative electrode material for lithium secondary battery |
KR100529069B1 (en) * | 1999-12-08 | 2005-11-16 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
KR20010076586A (en) * | 2000-01-26 | 2001-08-16 | 김순택 | Negative active material for lithium secondary battery and method of preparing same |
DE60212544T2 (en) * | 2001-11-01 | 2007-06-06 | Mitsubishi Chemical Corp. | Modified propylene polymer, adhesive composition obtainable therefrom and adhesive comprising same |
KR100433822B1 (en) * | 2002-01-17 | 2004-06-04 | 한국과학기술연구원 | Metal-coated carbon, preparation method thereof, and composite electrode and lithium secondary batteries comprising the same |
US7618678B2 (en) * | 2003-12-19 | 2009-11-17 | Conocophillips Company | Carbon-coated silicon particle powders as the anode material for lithium ion batteries and the method of making the same |
US7785661B2 (en) * | 2003-12-19 | 2010-08-31 | Conocophillips Company | Methods of preparing composite carbon-graphite-silicon particles and using same |
WO2005114767A1 (en) | 2004-04-23 | 2005-12-01 | Lg Chem, Ltd. | Anode active material with improved electrochemical properties and electrochemical device comprising the same |
CN1326267C (en) * | 2005-05-27 | 2007-07-11 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
KR100709860B1 (en) | 2005-07-22 | 2007-04-23 | 삼성에스디아이 주식회사 | Electrode including si material layer and porous layer and the lithium battery employing the same |
US20070092429A1 (en) * | 2005-10-24 | 2007-04-26 | Conocophillips Company | Methods of preparing carbon-coated particles and using same |
CN101572302B (en) * | 2009-03-07 | 2013-01-09 | 垦利三合新材料科技有限责任公司 | Method for preparing cathode materials of power lithium ion secondary batteries |
CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
KR101084069B1 (en) | 2010-06-17 | 2011-11-16 | 삼성에스디아이 주식회사 | Crystalline carbonaceous material with controlled interlayer spacing and method of preparing same |
CN101887966B (en) * | 2010-06-18 | 2012-12-05 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method of composite hard carbon cathode material of lithium ion battery |
CN101916845B (en) * | 2010-08-05 | 2012-12-05 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
CN101916856B (en) * | 2010-08-05 | 2012-12-05 | 深圳市贝特瑞新能源材料股份有限公司 | Cathode material for lithium-ion power and energy storage battery and preparation method thereof |
KR101182273B1 (en) * | 2010-08-12 | 2012-09-12 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, methode of preparing the same, and rechargeable lithium battery including the same |
CN113422023B (en) * | 2021-06-25 | 2023-03-03 | 洛阳月星新能源科技有限公司 | Modified natural graphite negative electrode material for power battery and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0239410A2 (en) * | 1986-03-27 | 1987-09-30 | Sharp Kabushiki Kaisha | An electrode and a battery with the same |
EP0334501A1 (en) * | 1988-03-04 | 1989-09-27 | Sharp Kabushiki Kaisha | Process for producing graphite electrodes |
EP0346088A1 (en) * | 1988-06-08 | 1989-12-13 | Sharp Kabushiki Kaisha | Electrode and method for its production |
EP0419090A1 (en) * | 1989-09-06 | 1991-03-27 | Sharp Kabushiki Kaisha | Carbon electrode |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863818A (en) * | 1986-06-24 | 1989-09-05 | Sharp Kabushiki Kaisha | Graphite intercalation compound electrodes for rechargeable batteries and a method for the manufacture of the same |
-
1993
- 1993-02-04 JP JP1759893A patent/JP2999085B2/en not_active Expired - Fee Related
- 1993-02-04 DE DE69302596T patent/DE69302596T2/en not_active Expired - Fee Related
- 1993-02-04 EP EP93300813A patent/EP0555080B1/en not_active Expired - Lifetime
-
1994
- 1994-10-17 US US08/323,572 patent/US5595838A/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0239410A2 (en) * | 1986-03-27 | 1987-09-30 | Sharp Kabushiki Kaisha | An electrode and a battery with the same |
EP0334501A1 (en) * | 1988-03-04 | 1989-09-27 | Sharp Kabushiki Kaisha | Process for producing graphite electrodes |
EP0346088A1 (en) * | 1988-06-08 | 1989-12-13 | Sharp Kabushiki Kaisha | Electrode and method for its production |
EP0419090A1 (en) * | 1989-09-06 | 1991-03-27 | Sharp Kabushiki Kaisha | Carbon electrode |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1422773A1 (en) * | 1993-10-08 | 2004-05-26 | Electro Energy, Inc. | Metal coated active material particles for battery electrodes |
CN100409468C (en) * | 1993-10-08 | 2008-08-06 | 电能公司 | Bipolar electrochemical battery of stacked wafer cells |
EP0833398A1 (en) * | 1996-09-24 | 1998-04-01 | PETOCA, Ltd | Surface graphitized carbon material, process for producing the same and negative electrode for lithium-ion secondary battery using the carbon material |
US6022518A (en) * | 1996-09-24 | 2000-02-08 | Petoca, Ltd. | Surface graphitized carbon material and process for producing the same |
EP1045465A2 (en) * | 1999-04-14 | 2000-10-18 | Sony Corporation | Material for negative electrode and nonaqueous-electrolyte battery incorporating the same |
EP1045465A3 (en) * | 1999-04-14 | 2004-07-21 | Sony Corporation | Material for negative electrode and nonaqueous-electrolyte battery incorporating the same |
US7776472B2 (en) | 2006-01-16 | 2010-08-17 | Ls Mitron Ltd. | Anode material for secondary battery, method for producing the same and secondary batteries using the same |
Also Published As
Publication number | Publication date |
---|---|
DE69302596T2 (en) | 1996-09-26 |
DE69302596D1 (en) | 1996-06-20 |
JPH05299073A (en) | 1993-11-12 |
EP0555080B1 (en) | 1996-05-15 |
JP2999085B2 (en) | 2000-01-17 |
US5595838A (en) | 1997-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0555080B1 (en) | Carbon composite electrode material | |
US5080930A (en) | Thermal cvd for the production of an electrode comprising a graphite composition | |
US5776610A (en) | Carbon composite electrode material and method of making thereof | |
US5344726A (en) | Carbon anode for secondary battery | |
EP0251677B1 (en) | Graphite intercalation compound electrodes for rechargeable batteries and a method for the manufacture of the same | |
Dresselhaus et al. | Synthesis of graphite fibers and filaments | |
Morales et al. | Use of low-temperature nanostructured CuO thin films deposited by spray-pyrolysis in lithium cells | |
Benea et al. | Preparation and investigation of nanostructured SiC–nickel layers by electrodeposition | |
EP0239410B1 (en) | An electrode and a battery with the same | |
SandI et al. | New carbon electrodes for secondary lithium batteries | |
US20160111711A1 (en) | Silicon-contained material, negative electrode for use in non-aqueous electrolyte secondary battery, method of producing the same, non-aqueous electrolyte secondary battery, and method of producing the same | |
US20110001097A1 (en) | Silicon composite, making method, and non-aqueous electrolyte secondary cell negative electrode material | |
CN111164804B (en) | Silicon-based negative electrode material, preparation method thereof and lithium ion battery | |
Matsuoka et al. | Electrochemical properties of hydrogen storage alloys modified with foreign metals | |
WO2006130739A2 (en) | Graphitized carbon coatings for composite electrodes | |
JP2592152B2 (en) | Method for producing carbon electrode for non-aqueous lithium secondary battery | |
JPS6324555A (en) | Electrode and its manufacture | |
JPS63102167A (en) | Electrode and battery | |
JPH0712924B2 (en) | Powdery highly crystalline graphite containing iron group element or alloy containing it | |
JP3532115B2 (en) | Non-aqueous secondary battery | |
Hsieh et al. | Formation and field-emission properties of carbon nanofibers by a simplified thermal growth | |
JP3032533B2 (en) | Carbon body electrode | |
JPH08315824A (en) | Electrode and manufacture of electrode | |
JP2656003B2 (en) | Non-aqueous secondary battery | |
Kinoshita | Proceedings of the conference on electrochemistry of carbon allotropes: Graphite, fullerenes and diamond |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
17P | Request for examination filed |
Effective date: 19930916 |
|
17Q | First examination report despatched |
Effective date: 19950213 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REF | Corresponds to: |
Ref document number: 69302596 Country of ref document: DE Date of ref document: 19960620 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20070131 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070201 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20070208 Year of fee payment: 15 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20080204 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20081031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080902 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080204 |